CN109821503B

CN109821503B - Uranium adsorption material and preparation method and application thereof

Info

Publication number: CN109821503B
Application number: CN201910234389.9A
Authority: CN
Inventors: 吴荣臻; 韩臻
Original assignee: Individual
Current assignee: Individual
Priority date: 2019-03-26
Filing date: 2019-03-26
Publication date: 2020-04-21
Anticipated expiration: 2039-03-26
Also published as: CN109821503A

Abstract

The embodiment of the invention discloses a uranium adsorption material and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing ferric iron salt hydrate, divalent magnesium salt hydrate and acetate to obtain a mixture; adding a polyhydroxy compound into the mixture, stirring and carrying out ultrasonic treatment to obtain a mixed solution; heating the mixed solution to 160-180 ℃, and carrying out heat preservation and sealing reaction for 8-10 h; centrifuging or magnetically separating the reacted mixed solution, collecting precipitates, washing and drying in vacuum to obtain the uranium adsorbing material; the preparation method of the invention prepares the uranium adsorbing material through specific raw materials, so that the uranium adsorbing material has excellent magnetic property and adsorption property and high yield, and the preparation method is simple to operate, low in cost and convenient for industrial production.

Description

Uranium adsorption material and preparation method and application thereof

Technical Field

The embodiment of the invention relates to the technical field of uranium adsorption, and particularly relates to a uranium adsorption material and a preparation method and application thereof.

Background

The nuclear energy is one of the most important clean energy sources in the 21 st century, and has stable energy supply which is higher than that of hydroelectric power, thermal power and wind power; the carbon emission is low, is lower than that of hydroelectric power and thermal power, and is equivalent to that of wind power; long service life and the like. However, the development of nuclear power in China is still in a low level at present, the power generation amount of commercial nuclear power plants in China in 2017 only accounts for 3.94% of the national power generation amount, and the data is expected to rise to 5.6% in 2020, but the data is still in the back row in more than 30 nuclear power development countries.

Among the factors that restrict the development of nuclear energy, the source of nuclear fuel and the disposal of highly radioactive spent fuel generated after the nuclear fuel is used are the most prominent. The recycling of low-concentration uranium in the spent fuel can increase the utilization rate of the uranium and effectively reduce the radiation hazard of the spent fuel, the current common extraction and treatment method uses a tributyl phosphate solvent extraction method, the method needs 3 extraction cycles, and is complex in operation, complex in process and high in cost.

In addition, the uranium content in seawater is as high as 45 hundred million tons, which is thousands of times of the storage amount of uranium ore on land. The technology of extracting uranium from seawater is firstly proposed and implemented by the Japan atomic energy organization, and then relevant research projects are set up in various countries in the world. But at present, most of the materials are in the experimental stage due to the cost and performance stability of the related materials; the novel sea water uranium extraction membrane material based on a metal-porphyrin ring structure, which is published in the top-level journal EES (Energy & environmental Scenece) under the RSC flag at 11-month Sichuan university in 2018, has the adsorption amount of about 140mg/g for low-concentration uranium (the concentration of uranyl ions is 1mmol/L), and can be recycled for multiple times. However, the preparation schemes of the materials are complicated and complex, the cost is expensive, the materials are not suitable for large-scale industrial production at present and are still in the research stage at present. The current uranium extracting material from seawater which can be used for industrial production is an activated carbon-titanium hydroxide composite material developed by the Japan atomic energy organization in 1971, the adsorption amount of the material to uranyl ions is only 1mg/g, and the adsorption amount is low.

Disclosure of Invention

Therefore, a first purpose of the embodiments of the present invention is to provide a uranium adsorbing material, so as to solve the problems in the prior art that the preparation of the uranium adsorbing material is complex, the adsorbing amount is low, and the cost is high.

The second purpose of the embodiment of the invention is to provide a preparation method of a uranium adsorbing material, which is simple to operate; the prepared uranium adsorption material has excellent adsorption performance and magnetic performance on uranyl ions, is low in cost and is convenient for industrial production.

The third purpose of the embodiment of the invention is to provide an application of a uranium adsorption material in adsorption of uranyl ions in a solution, the application can effectively adsorb the uranyl ions in the solution, and the adsorption amount reaches 169.5 mg/g.

In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:

according to a first aspect of the embodiments of the present invention, there is provided a preparation method of a uranium adsorption material, including the following steps:

(a) mixing ferric iron salt hydrate, divalent magnesium salt hydrate and acetate to obtain a mixture;

(b) adding a polyhydroxy compound into the mixture, stirring and carrying out ultrasonic treatment to obtain a mixed solution;

(c) heating the mixed solution to 160-180 ℃, and carrying out heat preservation and sealing reaction for 8-10 h;

(d) and centrifuging or magnetically separating the reacted mixed solution, collecting the precipitate, washing and drying in vacuum to obtain the uranium adsorbing material.

According to the method, the uranium adsorbing material is prepared by selecting the ferric iron salt hydrate, the divalent magnesium salt hydrate, the acetate and the polyhydroxy compound as raw materials, so that the uranium adsorbing material has excellent magnetic property and adsorption property, and the manufacturing cost is low; in addition, the invention can promote the growth of the nano material, improve the yield and avoid reducing the yield excessively by controlling the reaction conditions; in addition, the preparation method is simple to operate and convenient for industrial production.

Further, in the step (b), the stirring speed is 360-; stirring for 25-35 min;

further, in the step (b), the ultrasonic frequency adopted by the ultrasonic treatment is 45000-50000 HZ; the treatment time is 15-25 min.

According to the invention, through stirring and ultrasonic treatment, all raw materials can be fully and uniformly mixed, so that the full reaction among the raw materials can be improved, and the yield can be improved.

Further, in the step (d), the centrifugation speed is 8000-; the washing agent is methanol, and the washing times are 2-4 times. According to the invention, through centrifugation and washing treatment, impurities such as a solvent on the surface of the prepared uranium adsorption material can be removed, and the purity is improved.

Further, the molar ratio of the ferric iron salt hydrate to the divalent magnesium salt hydrate is 10 to (1-6).

Further, the molar ratio of the hydrate of the ferric iron salt to the acetate is 1 to (8-10).

Further, the concentration of the hydrate of the ferric iron salt in the mixed solution is 0.05-0.083 mol/L.

According to the invention, the use amount of each raw material is further limited, so that the adsorption performance and the magnetic performance of the prepared uranium adsorption material can be better improved.

Further, the ferric salt hydrate is selected from any one of ferric chloride hydrate, ferric bromide hydrate, ferric nitrate hydrate and ferric sulfate hydrate.

Further, the divalent magnesium salt hydrate is selected from any one of water and magnesium chloride, hydrated magnesium bromide, hydrated magnesium nitrate and hydrated magnesium acetate.

Further, the acetate is selected from sodium acetate or ammonium acetate.

Further, the polyol is selected from any one or more of ethylene glycol, glycerol and propylene glycol.

According to a second aspect of the embodiments of the present invention, there is provided a uranium adsorbing material, which is prepared by the above preparation method.

Furthermore, the uranium adsorption material is of a sheet structure, the thickness of the uranium adsorption material is 5-10nm, and the length of the uranium adsorption material is 1-4 um.

The uranium adsorption material has excellent adsorption performance on uranyl ions, can efficiently adsorb the uranyl ions, has stronger magnetic performance, and can realize rapid recovery of the uranium adsorption material; in addition, the uranium adsorption material can be stored in a sealed manner at room temperature by adopting nitrogen or argon under a dry condition, or stored in a sealed manner by adopting methanol or ethanol for soaking, or stored by using a vacuum packaging bag, low-temperature refrigeration is not needed, and the storage is convenient.

According to a third aspect of the embodiments of the present invention, there is provided a method for adsorbing uranyl ions in a solution, the method using the uranium adsorbent material for adsorption.

The embodiment of the invention has the following advantages:

(1) according to the preparation method, the uranium adsorbing material is prepared from the specific raw materials, so that the uranium adsorbing material has excellent magnetic property and adsorption property, and the preparation cost is low;

(2) the preparation method disclosed by the invention can promote the growth of the nano material, improve the yield and avoid reducing the yield excessively by controlling the reaction conditions, and is simple to operate and convenient for industrial production.

(3) The uranium adsorption material has excellent adsorption performance on uranyl ions, can efficiently adsorb the uranyl ions, has stronger magnetic performance, and can realize rapid recovery of the uranium adsorption material; in addition, the uranium adsorption material can be stored in a sealed manner at room temperature by adopting nitrogen or argon under a dry condition, or stored in a sealed manner by adopting methanol or ethanol for soaking, or stored by using a vacuum packaging bag, low-temperature refrigeration is not needed, and the storage is convenient.

(4) The uranium adsorption material can be used for recognizing effective adsorption of uranyl ions after desorption, and realizes reutilization.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.

FIG. 1 is an SEM atlas of a uranium adsorbing material prepared in example 3 of the invention;

FIG. 2 is an EDS spectrum of a uranium adsorbing material prepared in example 3 of the present invention;

fig. 3 is an element mapping map of the uranium adsorbing material prepared in example 3 of the present invention;

FIG. 4 is a mapping map of magnesium element of the uranium adsorbing material prepared in example 3 of the present invention;

fig. 5 is an iron element mapping map of the uranium adsorbing material prepared in example 3 of the present invention;

fig. 6 is a mapping map of carbon elements of the uranium adsorbing material prepared in example 3 of the present invention;

FIG. 7 is an oxygen mapping map of a uranium adsorbing material prepared in example 3 of the present invention;

FIG. 8 is an XPS spectrum of a uranium adsorbing material prepared in example 3 of the present invention;

FIG. 9 is an enlarged spectrum between 740 and 700eV in an XPS spectrum of a uranium adsorbing material prepared in example 3 of the present invention;

FIG. 10 is an enlarged spectrum between 298-279eV in an XPS spectrum of a uranium adsorbing material prepared in example 3 of the present invention;

FIG. 11 is an enlarged spectrum between 1309-1296eV in an XPS spectrum of a uranium adsorbing material prepared in example 3 of the present invention;

FIG. 12 is an enlarged spectrum between 545-525eV in an XPS spectrum of a uranium adsorbing material prepared in example 3 of the present invention;

FIG. 13 is a thermogravimetric analysis curve of a uranium adsorbing material prepared in example 3 of the present invention;

fig. 14 is an EDS spectrum of a uranium adsorbing material that adsorbs uranyl ions in experimental example 1 of the present invention;

fig. 15 is an element mapping map of a uranium adsorbing material for adsorbing uranyl ions in experimental example 1 of the present invention;

fig. 16 is a mapping map of uranium elements in the uranium adsorbing material for adsorbing uranyl ions in experimental example 1 of the present invention;

fig. 17 is a carbon element mapping map of the uranium adsorbing material for adsorbing uranyl ions in experimental example 1 of the present invention;

fig. 18 is an oxygen element mapping map of the uranium adsorbing material for adsorbing uranyl ions in experimental example 1 of the present invention;

fig. 19 is a mapping map of magnesium element of the uranium adsorbing material for adsorbing uranyl ions in experimental example 1 of the present invention;

fig. 20 shows an iron element mapping map of the uranium adsorbent that adsorbs uranyl ions in experimental example 1 of the present invention.

Detailed Description

The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The embodiment is a preparation method of a uranium adsorption material, and the preparation method comprises the following steps:

(a) mixing hydrated ferric chloride, hydrated magnesium bromide and sodium acetate to obtain a mixture, wherein the molar ratio of the hydrated ferric chloride to the hydrated magnesium bromide is 10: 2.5; the molar ratio of the hydrated ferric chloride to the sodium acetate is 1: 8;

(b) adding glycerol into the mixture, stirring for 25min at 600r/min, and performing ultrasonic treatment for 25min at 45000HZ ultrasonic wave to obtain a mixed solution, wherein the concentration of the hydrated ferric chloride in the mixed solution is 0.06 mol/L;

(c) heating the mixed solution to 160 ℃, and carrying out heat preservation and closed reaction for 10 hours;

(d) centrifuging the reacted mixed solution at 8000r/min for 10min, collecting precipitate, adding methanol into the precipitate, stirring, centrifuging, collecting precipitate, repeating the steps of adding methanol, stirring, centrifuging, collecting precipitate for 1 time, and vacuum drying the collected precipitate to obtain the uranium adsorbing material. The material has good magnetism.

And weighing the obtained uranium adsorption material, and calculating the yield according to the yield which is the weight of the uranium adsorption material/the mass of a theoretical product multiplied by 100%, wherein the mass of the theoretical product is the mass of methyl carbon in added sodium acetate, the mass of theoretical ferroferric oxide and the mass of theoretical magnesium oxide. The amount of methyl carbon in the added sodium acetate is (mass of sodium acetate/molar mass of sodium acetate). times.12; theoretical ferroferric oxide mass ═ (hydrated iron salt mass/hydrated iron salt molar mass) ÷ 3 × ferroferric oxide molar mass; theoretical magnesium oxide mass ═ (mass of hydrated magnesium salt/molar mass of hydrated magnesium salt) × magnesium oxide molar mass. The settlement yield result was 58.42%.

Example 2

(a) mixing hydrated ferric bromide, hydrated magnesium chloride and ammonium acetate to obtain a mixture, wherein the molar ratio of the hydrated ferric bromide to the hydrated magnesium chloride is 10: 5.5; the molar ratio of hydrated ferric bromide to ammonium acetate is 1: 10;

(b) adding propylene glycol into the mixture, stirring for 35min at 360r/min, and performing ultrasonic treatment for 15min at 50000HZ ultrasonic wave to obtain a mixed solution, wherein the concentration of hydrated ferric bromide in the mixed solution is 0.083 mol/L;

(c) heating the mixed solution to 170 ℃, and carrying out heat preservation and sealing reaction for 8 hours;

(d) centrifuging the reacted mixed solution for 5min at 12000r/min, collecting precipitate, adding methanol into the precipitate, stirring, centrifuging, collecting precipitate, repeating the operations of adding methanol, stirring, centrifuging, collecting precipitate for 3 times, and vacuum drying the collected precipitate to obtain the uranium adsorbing material with general magnetism.

The yield of uranium adsorbent material in the above preparation method was calculated according to the calculation method of example 1, and the calculated yield was 53.21%.

Example 3

(a) mixing ferric chloride hydrate, magnesium chloride hydrate and sodium acetate to obtain a mixture, wherein the molar ratio of the ferric chloride hydrate to the magnesium chloride hydrate is 10: 3; the molar ratio of the hydrated ferric chloride to the sodium acetate is 1: 9;

(b) adding ethylene glycol into the mixture, stirring for 30min at 500r/min, and performing ultrasonic treatment for 20min at 50000HZ ultrasonic wave to obtain a mixed solution, wherein the concentration of the hydrated ferric chloride in the mixed solution is 0.05 mol/L;

(c) heating the mixed solution to 180 ℃, and carrying out heat preservation and sealed reaction for 9 hours;

(d) centrifuging the reacted mixed solution at 10000r/min for 8min, collecting precipitates, adding methanol into the precipitates, stirring, centrifuging, collecting the precipitates, repeating the operations of adding methanol, stirring, centrifuging, collecting the precipitates for 2 times, and drying the collected precipitates in vacuum to obtain the uranium adsorbing material with good material magnetism.

The yield of uranium adsorbent material in the above preparation method was calculated according to the calculation method of example 1, and the calculated yield was 66.50%.

Detecting the prepared uranium adsorbing material to respectively obtain an SEM (scanning electron microscope) map, an EDS (enhanced dispersive spectroscopy) map, an element mapping map, TG thermogravimetric analysis and X-ray photoelectron spectroscopy XPS (X-ray photoelectron spectroscopy) of the uranium adsorbing material;

wherein, the SEM atlas is shown in figure 1, and as can be seen from figure 1, the uranium adsorption material has a sheet structure, the thickness is 5-10nm, and the length is 1-4 um.

As shown in fig. 2, the EDS spectrum of the uranium adsorbent shown in fig. 2 indicates that the uranium adsorbent includes four elements, i.e., oxygen, iron, magnesium, and carbon.

The mapping patterns of the elements are shown in fig. 3-7, and it can be known from fig. 3-7 that four elements of oxygen, iron, magnesium and carbon are uniformly distributed in the nanospheres.

As shown in fig. 8 to 11, it can be seen from fig. 8 to 11 that the iron element in the material exists in two valence states, namely, a positive divalent valence state and a positive trivalent valence state (a peak value at 710eV and a satellite peak value at about 725 eV), the magnesium element mainly exists in a positive divalent state (a peak value at about 1303.2 eV), the carbon element mainly exists in a zero valence state (a peak value at 284.6 eV), and the oxygen element mainly exists in a negative divalent state (a peak value at about 530 eV), so that the material can be inferred to be the simple substance carbon-ferroferric oxide-magnesium oxide composite nanomaterial.

Thermogravimetric analysis is carried out on the uranium adsorbing material prepared by the method under the protection of argon by using a thermogravimetric analyzer, the analysis result is shown in fig. 12, as can be seen from fig. 12, the uranium adsorbing material contains simple substance carbon, and exothermic peak and mass reduction phenomenon at about 319.73 ℃ are derived from reduction of ferroferric oxide and magnesium oxide by carbon element (nano size enables the reduction reaction to occur at a lower temperature).

Example 4

This example is a method of manufacturing a uranium adsorbent material, which is substantially the same as that of example 3, except that the molar ratio of hydrated ferric chloride to hydrated magnesium chloride is 10: 2.

The yield of uranium adsorbent material in the above preparation method was calculated according to the calculation method of example 1, and the calculated yield was 64.82%.

Example 5

This example is a method of manufacturing a uranium adsorbent material, which is substantially the same as that of example 3, except that the molar ratio of hydrated ferric chloride to hydrated magnesium chloride is 10: 6.

The yield of uranium adsorbent material in the above preparation method was calculated according to the calculation method of example 1, and the calculated yield was 67.18%.

Comparative example 1

The present comparative example is a method for producing a uranium adsorbent, and the production method is substantially the same as that of example 3, except that in step (c), the mixed solution is heated to 150 ℃.

The yield of uranium adsorbent material in the above preparation method was calculated according to the calculation method of example 1, and the calculated yield was 41.24%.

Experimental example 1

Respectively selecting 0.05g of uranium adsorbing materials prepared in examples 1-5 and comparative example 1; respectively putting the selected uranium adsorption materials into 50ml of 1mmol/L uranyl nitrate solution with the pH value of 5 (the pH value is adjusted to 5 by using sodium hydroxide and 2mol/L dilute nitric acid), and shaking the table for 24 hours; subsequently, 2ml of each solution was centrifuged, and 1ml of the supernatant was diluted 10 times, and the uranium element concentration C was measured by ICP-OES. Adsorbing capacity is V x (C) according to the formula₀-C) ÷ mass of uranium adsorbing material, (V is the volume of the solution, equal to 50 ml; c₀Starting concentration of uranium, equal to 238 mg/L; ) And respectively calculating the uranium adsorption amount of the uranium adsorption material prepared in each embodiment, repeating the operation for 5 times, and counting the average value of the adsorption amounts of the uranium adsorption materials prepared in each embodiment, wherein the statistical result is shown in table 1:

TABLE 1

From table 1 in combination with the experimental phenomena in the examples, it can be seen that:

the uranium adsorption material prepared by the method can efficiently adsorb uranyl ions, and the maximum uranium adsorption material can be 169.5 mgU/g; and the molar ratio of the hydrated ferric chloride to the hydrated magnesium chloride directly influences the adsorption effect of the uranyl ions and the material magnetism, when the molar ratio of the hydrated ferric chloride to the hydrated magnesium chloride is out of 10 to (3-4.5), the adsorption effect is reduced sharply when the molar ratio is less than 10 to 3, and the adsorption effect is not reduced greatly but the material magnetism is reduced seriously when the molar ratio is more than 10 to 4.5.

Selecting the uranium adsorption material prepared in the embodiment 3 after adsorbing the uranyl ions, and detecting the material to obtain an EDS (enhanced data System) map and an element mapping map;

the EDS spectrum is shown in fig. 14, and it can be seen from fig. 14 that the uranium adsorbent includes five elements of uranium, oxygen, iron, magnesium, and carbon.

The mapping spectrum of the elements is shown in fig. 15-20, and it can be known from fig. 15-20 that uranium, oxygen, iron, magnesium and carbon are uniformly distributed in the nanospheres.

Experimental example 2

The uranium adsorption material prepared in the embodiment 3 is selected, and the uranium adsorption material is averagely divided into 10 parts, wherein each part is 0.02 g;

then, respectively measuring ten 50ml of 1mmol/L uranyl nitrate solution with the pH value of 5 (adjusting the pH value by using sodium hydroxide and 2mol/L dilute nitric acid); then, respectively putting the uranium adsorption materials into uranyl nitrate solution, and oscillating in a shaking table; and then 2ml of solution is taken from 1h, 2h, 3h, 6h, 9h, 12h, 24h and 36h of the 1-10 groups respectively for centrifugation, 1ml of supernatant is taken and diluted by 10 times, and the concentration C of the uranium element is determined by adopting ICP-AES. The uranium adsorption amount of the uranium adsorption material prepared in each example was calculated according to the formula of adsorption amount × (C0-C) ÷ uranium adsorption material mass, (V is solution volume, equal to 50ml, and C0 is initial uranium element concentration, equal to 238mg/L), and the above operation was repeated 5 times, and the average value of the adsorption amount of the uranium adsorption material prepared in each example was counted, and the statistical results are shown in table 2:

TABLE 2

Time of day	1h	2h	3h	6h	9h	12h	24h	36h
									Adsorption Capacity (mg/g)	8.4	12.1	18.3	27.5	58.4	81.4	128.7	170.3

As can be seen from Table 2: the uranium adsorption material has higher adsorption capacity, and the adsorption capacity is steadily increased along with the increase of the adsorption time. The adsorption capacity reaches 169.5mgU/g after 36 hours. The adsorption curve is still rising steadily, and the uranyl ion adsorption capacity of the material has great potential.

Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. A preparation method of a uranium adsorption material is characterized by comprising the following steps:

(a) mixing ferric salt hydrate, divalent magnesium salt hydrate and acetate to obtain a mixture, wherein the molar ratio of the ferric salt hydrate to the divalent magnesium salt hydrate is 10: 1-6, the molar ratio of the ferric salt hydrate to the acetate is 1: 8-10, and the concentration of the ferric salt hydrate in the mixed solution is 0.05-0.083 mol/L; the ferric salt hydrate is selected from any one of ferric chloride hydrate, ferric bromide hydrate, ferric nitrate hydrate and ferric sulfate hydrate; the divalent magnesium salt hydrate is selected from any one of hydrated magnesium chloride, hydrated magnesium bromide, hydrated magnesium nitrate and hydrated magnesium acetate; the acetate is selected from sodium acetate or ammonium acetate;

(b) adding a polyhydroxy compound into the mixture, stirring and carrying out ultrasonic treatment to obtain a mixed solution, wherein the polyhydroxy compound is any one or more of ethylene glycol, glycerol and propylene glycol;

2. A uranium adsorbing material, characterized by being prepared by the preparation method of claim 1.

3. A method for adsorbing uranyl ions in a solution, characterized in that the adsorption is carried out by using the uranium adsorbent material according to claim 2.